Articles formed of pulp base materials with modulated scent release

ABSTRACT

Described are articles formed of a pulp base material comprising fibers, wherein pores are formed between the fibers. A volatile composition with at least one top note component and at least one base note component at least partially fills the pores of the pulp base material. A release rate of the at least one top note component is modulated by the pulp base material, and a release rate of the at least one base note component is enhanced by the pulp base material.

CROSS REFERENCE TO RELATED APPLICATION

This application is related to and claims priority benefit from U.S.Provisional Application No. 62/402,906 (“the '906 application”), filedon Sep. 30, 2016, entitled ARTICLES FORMED OF PULP BASE MATERIALS WITHMODULATED SCENT RELEASE. The '906 application is hereby incorporated inits entirety by this reference.

FIELD OF THE INVENTION

The field of the invention relates to articles formed of pulp basematerials, which are configured to provide a modulated release ofvolatile compositions, and more specifically relates to articles formedof pulp base materials that provide a modulated release of volatileolfactory or fragrance compounds.

BACKGROUND

Fragrance-releasing devices are well known and commonly used inhousehold and commercial establishments to provide a pleasantenvironment for people in the immediate space. Further, aroma-drivenexperiences are well recognized to improve or enhance the general moodof individuals. In some instances, fragrances may trigger memories ofexperiences associated with the specific scent. Whether it is providinga pleasant environment, affecting a general demeanor, or triggering anostalgic memory, a steady, long-lasting release of fragrance willensure consumer and customer satisfaction.

Fragrance-release devices based on passive diffusion are limited intheir product-use by a finite supply of the fragrance and itsevaporation rate from a surface. In some examples, the fragrance-releasedevice is designed to carry the fragrance liquid within its architectureso that the fragrance supply is finite and determined by the size of thefragrance-release device.

The evaporation rate of fragrance from the fragrance-release device isdetermined, at least in part, by the composition of the fragrance, wherecompositions containing more volatile compounds (e.g. “top” notes) willevaporate faster than those with less volatile compounds (e.g. “base”notes). A fragrance composition determines its character. As a result,changing the composition of the fragrance will affect the character. Therelease rate profile of fragrance is generally strong (more intense) atthe beginning of product use, followed by decreasing intensity overtime.

For these fragrances, there is a need to modulate the release offragrance from the fragrance-release device to provide a steady andlong-lasting fragrance release without changing the fragrance load andcharacter. Specifically, there is a need to temper the release offragrance compounds at the initial stage of product use, followed byfacilitation of fragrance compound release at a later stage of productuse. There is also a need to modulate the type of scent released overtime so that the olfactory senses do not become immune to the scentreleased by the article.

SUMMARY

The terms “invention,” “the invention,” “this invention” and “thepresent invention” used in this patent are intended to refer broadly toall of the subject matter of this patent and the patent claims below.Statements containing these terms should be understood not to limit thesubject matter described herein or to limit the meaning or scope of thepatent claims below. Embodiments of the invention covered by this patentare defined by the claims below, not this summary. This summary is ahigh-level overview of various aspects of the invention and introducessome of the concepts that are further described in the DetailedDescription section below. This summary is not intended to identify keyor essential features of the claimed subject matter, nor is it intendedto be used in isolation to determine the scope of the claimed subjectmatter. The subject matter should be understood by reference toappropriate portions of the entire specification of this patent, any orall drawings and each claim.

According to certain embodiments of the present invention, an articlecomprises a pulp base material comprising fibers, wherein pores areformed between the fibers, and a volatile composition comprising atleast one top note component and at least one base note component. Thevolatile composition at least partially fills the pores of the pulp basematerial, wherein a release rate of the at least one top note componentis modulated by the pulp base material, and wherein a release rate ofthe at least one base note component is enhanced by the pulp basematerial.

In some embodiments, the pulp base material comprises at least one lowporosity zone and at least one high porosity zone. The at least one topnote component may be added to the at least one low porosity zone, andthe at least one base note component may be added to the at least onehigh porosity zone.

The at least one low porosity zone and the at least one high porosityzone may be formed by use of a mold having different drainage surfaces,by use of a divider within a mold, by application of different pressuresto portions of a mold, by application of different pulp concentrationsto portions of a mold, and/or by application of different amounts of gasor gas-forming materials to portions of the pulp base material. In someembodiments, the at least one low porosity zone is formed in a firstmold and the at least one high porosity zone is formed in a second mold.

The article may comprise at least two pulp base materials joinedtogether.

In some embodiments, the pulp base material comprises at least onesurface having complex geometry. The complex geometry may comprise peaksand flatter regions. The peaks may enhance the release rate of thevolatile composition and/or provide three-dimensional emission of thevolatile composition.

The article may comprise an attachment element. The attachment elementmay comprise a hole.

The article may comprise a smooth surface for holding the article in anupright position. In some embodiments, a stand is coupled to the articleto hold the article in an upright position.

A backing layer may be added to the article. The backing layer may beformed of a conductive material.

In some embodiments, the article may further comprise an opening throughthe article for placement of a light source.

In certain embodiments, the pulp base material comprises a firstporosity and openings in which other materials having at least a secondporosity are added to the pulp base material.

A modulating coating may applied to the pulp base material, only appliedto the at least one low porosity zone, and/or only applied to the atleast one high porosity zone.

In some embodiments, the article is combined with at least one energysource.

The at least one energy source may be a warmer bowl or plate and/or afan. The article may form at least one blade of the fan.

In some embodiments, the article is positioned around a light source.

In some embodiments, the article is positioned within a supportstructure.

BRIEF DESCRIPTION OF THE DRAWINGS

In the following detailed description, embodiments of the invention aredescribed referring to the following figures:

FIG. 1 is an image of a mold used to form a pulp base material,according to certain embodiments of the present invention.

FIG. 2 is a top view of the pulp base material formed with the mold ofFIG. 1.

FIG. 3 is a side view of the pulp base material of FIG. 1.

FIG. 4 is a top view of a pulp base material formed with a divider,according to certain embodiments of the present invention.

FIG. 5 is a side view of a pulp base material formed with a divider inwhich the top and bottom surfaces of the divider are covered by pulpmaterial, according to certain embodiments of the present invention.

FIG. 6 is a side view of a pulp base material formed with a divider inwhich the top surface of the divider are covered by pulp material,according to certain embodiments of the present invention.

FIG. 7 is a side view of a pulp base material formed with a divider inwhich the top and bottom surfaces of the divider are not covered by pulpmaterial, according to certain embodiments of the present invention.

FIG. 8 is a side view of a pulp base material formed with a dividercomprising a backing layer, according to certain embodiments of thepresent invention.

FIG. 9 is a top view of a pulp base material formed with a dividercomprising multiple zones, according to certain embodiments of thepresent invention.

FIG. 10 is a flow diagram of a multi-step molding process, according tocertain embodiments of the present invention.

FIG. 11 is a side view of a pulp base material formed with complexsurface geometry, according to certain embodiments of the presentinvention.

FIG. 12 is a side view of a pulp base material formed with complexsurface geometry, according to certain embodiments of the presentinvention.

FIG. 13 is a top view of a pulp base material formed with an attachmentelement, according to certain embodiments of the present invention.

FIG. 14 is a top view of a pulp base material formed with an opening,according to certain embodiments of the present invention.

FIG. 15 is a top view of a pulp base material formed with a plurality ofopenings for addition of other materials, according to certainembodiments of the present invention.

FIG. 16 is a top view of the pulp base material of FIG. 15 with theother materials incorporated into the plurality of openings.

FIG. 17 is a side view of two pulp base materials being joined,according to certain embodiments of the present invention.

FIG. 18 is a side view of the two pulp base materials of FIG. 17 joined.

FIG. 19 is a side view of a pulp base material with a capillary systemfor introduction of volatile compositions into the pulp base material.

FIG. 20 includes front images of articles with attachment elements and avariety of shapes, according to certain embodiments of the presentinvention.

FIG. 21 includes front images of articles with attachment elements and avariety of shapes, according to certain embodiments of the presentinvention.

FIG. 22 includes front and side images of articles with attachmentelements and a variety of shapes, according to certain embodiments ofthe present invention.

FIG. 23 includes front images of articles with attachment elements thatcouple the articles to stands, according to certain embodiments of thepresent invention.

FIG. 24 is a front image of an article and an attachable backing layer,according to certain embodiments of the present invention.

FIG. 25 is a front view of the article of FIG. 24 attached to thebacking layer.

FIG. 26 is a rear view of the article of FIG. 24 attached to the backinglayer.

FIG. 27 is a sketch of an article with an attachable backing layer.

FIG. 28 includes front and side images of articles with attachmentelements and a variety of shapes and coloration, according to certainembodiments of the present invention.

FIG. 29 is a sketch of an article with an attached backing layer.

FIG. 30A includes front and side images of articles with attachmentelements and a variety of shapes and coloration, along with a side imageof an article formed by joining two pulp base materials, according tocertain embodiments of the present invention.

FIG. 30B includes front images of articles with attachment elements anda variety of shapes and coloration, according to certain embodiments ofthe present invention.

FIG. 31 includes top, front, and side views of an article formed byjoining two pulp base materials, according to certain embodiments of thepresent invention.

FIG. 32 includes top, front, and side views of an article formed byjoining two pulp base materials, according to certain embodiments of thepresent invention.

FIGS. 33A, 33B and 33C include images of an article formed by joiningtwo pulp base materials, according to certain embodiments of the presentinvention.

FIG. 34 is a front view of an article, according to certain embodimentsof the present invention.

FIG. 35 is a rear view of the article of FIG. 34 coupled to a stand.

FIG. 36 is a front view of the stand of FIG. 35.

FIG. 37 includes front and side images of articles with stands and avariety of shapes and coloration, according to certain embodiments ofthe present invention.

FIGS. 38A and 38B include front images of articles with stands and avariety of shapes, according to certain embodiments of the presentinvention.

FIG. 39A includes front and side images of articles with stands and avariety of shapes and coloration, according to certain embodiments ofthe present invention.

FIG. 39B includes front images of articles with stands and a variety ofshapes and coloration, according to certain embodiments of the presentinvention.

FIG. 40 includes top, front, side, and rear views of an article formedby joining two pulp base materials, according to certain embodiments ofthe present invention.

FIGS. 41A, 41B, and 41C include top and side views of articles withstands and a variety of shapes, according to certain embodiments of thepresent invention.

FIG. 42 includes side views of articles with stands, according tocertain embodiments of the present invention.

FIG. 43 includes top, side, and perspective views of an article with astand, according to certain embodiments of the present invention.

FIGS. 44A and 44B include top, side, and perspective views of an articlewith a stand, according to certain embodiments of the present invention.

FIG. 45 includes side views of articles combined with energy sources,according to certain embodiments of the present invention.

FIG. 46 includes side views of articles combined with energy sources,according to certain embodiments of the present invention.

FIG. 47 includes front views of articles with a variety of shapes andcoloration, according to certain embodiments of the present invention.

FIG. 48 includes front views of articles with a variety of shapes and awarmer bowl, according to certain embodiments of the present invention.

FIG. 49 includes front views of articles with a variety of shapes and awarmer bowl, according to certain embodiments of the present invention.

FIG. 50 includes top and side views of an article combined with abacking layer and holder, according to certain embodiments of thepresent invention.

FIGS. 51A and 51B include front and side images of articles with avariety of shapes and coloration and a plug-in heating element,according to certain embodiments of the present invention.

FIGS. 52A and 52B include front, side, and perspective images ofarticles with a variety of shapes and coloration and a plug-in heatingelement, according to certain embodiments of the present invention.

FIG. 53 includes front and side images of articles with a variety ofshapes and coloration and a plug-in heating element, according tocertain embodiments of the present invention.

FIGS. 54A and 54B include front, side, and perspective images ofarticles with a variety of shapes and coloration and a plug-in heatingelement, according to certain embodiments of the present invention.

FIGS. 55A and 55B include front, side, and perspective images ofarticles with a variety of shapes and coloration and a plug-in heatingelement, according to certain embodiments of the present invention.

FIGS. 56A and 56B include front, side, and perspective images ofarticles with a variety of shapes and coloration and a plug-in heatingelement, according to certain embodiments of the present invention.

FIG. 57 includes a sketch of an article forming blades of a fan,according to certain embodiments of the present invention.

FIG. 58 includes a sketch of an article forming blades of a fan,according to certain embodiments of the present invention.

FIG. 59 is a perspective view of a support structure for an article,according to certain embodiments of the present invention.

FIG. 60 is a top view of the support structure of FIG. 59.

FIG. 61 is a bottom view of the support structure of FIG. 59.

FIG. 62 is a front view of a decorative covering attached to the supportstructure of FIG. 59.

FIG. 63 is a side view of the decorative covering and support structureof FIG. 62.

FIG. 64 is a bottom view of the decorative covering and supportstructure of FIG. 62.

FIG. 65 is a schematic illustrating the movement of a volatilecomposition across an internal structure of a base material and amodulating coating over time, according to certain embodiments of thepresent invention.

FIG. 66 is a microphotograph image of a cross-section of a sample of athree-dimensional pulp object comprising a low density pulp basematerial, according to certain embodiments of the present invention.

FIG. 67 is a microphotograph image of a cross-section of a sample of athree-dimensional pulp object comprising a high density pulp basematerial, according to certain embodiments of the present invention.

FIG. 68 is a microphotograph image of a cross-section of a sample of athree-dimensional pulp object with both high density pulp material andlow density pulp material, according to certain embodiments of thepresent invention.

FIG. 69 is a microphotograph low-angle reflected light image of across-section of a sample of a three-dimensional pulp object comprisinga low density pulp base material after iodine staining, according tocertain embodiments of the present invention.

FIG. 70 is a microphotograph low-angle reflected light image of across-section of a sample of a three-dimensional pulp object comprisinga high density pulp base material after iodine staining, according tocertain embodiments of the present invention.

FIG. 71 is a high resolution image of the cross-section of the lowdensity sample of FIG. 69.

FIG. 72 is a high resolution image of the cross-section of the highdensity sample of FIG. 70.

FIG. 73 is a front view of an article, according to certain embodimentsof the present invention.

FIG. 74 is a rear view of the article of FIG. 73.

FIG. 75 is a front view of an article, according to certain embodimentsof the present invention.

FIG. 76 is a rear view of the article of FIG. 75.

FIG. 77 is a perspective assembled view of a support structure for anarticle, according to certain embodiments of the present invention.

FIGS. 78A and 78B are exploded perspective views of the supportstructure of FIG. 77.

FIG. 79 is a graph showing weight loss data for two density zonesaccording to certain embodiments of the present invention.

FIG. 80 is a graph showing weight loss data for an article according tocertain embodiments of the present invention.

DETAILED DESCRIPTION

The subject matter of embodiments of the present invention is describedhere with specificity to meet statutory requirements, but thisdescription is not necessarily intended to limit the scope of theclaims. The claimed subject matter may be embodied in other ways, mayinclude different elements or steps, and may be used in conjunction withother existing or future technologies. This description should not beinterpreted as implying any particular order or arrangement among orbetween various steps or elements except when the order of individualsteps or arrangement of elements is explicitly described.

According to certain embodiments of the present invention, an article 10comprises a base material 12.

A. Base Material

The base material 12 may comprise an internal structure 20 comprising aplurality of pores 22 that are configured to provide locations for thevolatile composition 24 to be stored therein and released therefrom,which is described in detail below.

The base material 12 may comprise natural and/or synthetic pulpcompositions; pulp compositions combined with other products, includingbut not limited to paper, cellulose, cellulose acetate, pulp lap, cottonlinters, biological plant-derived materials (from living plants),synthesized pulp compositions, and mixed pulps; polymer material; porousmaterial; and/or extrudate.

As known in the art, pulp is primarily a collection of fibers with othercomponents of the source material, wherein the fibers are derived from anatural or synthetic source material, for example, biological plants(natural) or petroleum-based synthesis products (synthetic). Pulp may beproduced from various types of woods using any one of several knownpulping techniques. The pulp may be from hardwoods, softwoods, ormixtures thereof. The pulp may also be produced from bamboo, sugarcane,and other pulp sources. The pulp may also be made from recycledmaterials, and comprises recovering waste paper and remaking it into newproducts.

In certain embodiments, the number and/or size of the plurality of pores22 (i.e., porosity) within the base material 12 may be controlled by thecompactness and/or size of the fibers and/or particles that form theinternal structure 20. For example, in certain embodiments of the basematerial 12 that comprise fibers, voids between the fibers form tiny airpassages throughout the internal structure 20. The compactness of thefibers affects the degree in which the base material 12 allows gas orliquid to pass through it. For example, porosity may affect absorbency,uptake, and/or load amount of volatile compositions, or may affect therate of release of such substances. Porosity and/or absorbency of thebase material 12 may be affected by adding other materials, such asadditives to the matrix material 12 as it is being formed from acomposition, such as pulp or any other composition described above, sothat the additives are located within the internal structure 20 of thebase material 12 after formation.

The porosity of a base material 12 that comprises pulp may be affectedat any stage of the pulp production process. An increased level of fiberrefining causes the fibers to bond together more strongly and tightly,making the pulp material denser, thereby reducing the network of airpassages and the porosity. The porosity of the base material 12 may alsobe controlled using other compression methods, which are described indetail below.

The porosity of the base material 12 is measured quantitatively aseither the length of time it takes for a quantity of air to pass througha sample, or the rate of the passage of air through a sample, usingeither a Gurley densometer (in the first case) or a Sheffieldporosimeter (in the second case). With the Gurley densometer, theporosity is measured as the number of seconds required for 100 cubiccentimeters of air to pass through 1.0 square inch of a given materialat a pressure differential of 4.88 inches of water, as described in ISO5646-5, TAPPI T-460, or TAPPI T-536.

The porosity may affect how completely and how quickly the volatilecomposition 24 is absorbed into a pulp base material 12, as suchabsorption may occur primarily by capillary action. For example, a pulpbase material 12 with high porosity may have increased absorbency of thevolatile composition 24. As an example relating porosity to standardtest methods for sheets of paper, the porosity of the pulp base material12 may range from 0.01 Gurley second—100 Gurley seconds, and all rangestherein. In certain embodiments where there are multiple layers of pulpbase material 12, the porosity may range from 0.01 Gurley second—20Gurley seconds. The volatile composition 24 may be applied to the basematerial 12 in the form of a film or a coating, or as a treatmentintegrated into the internal structure 20 of the base material 12. Thedifference in porosities affects the release rate of the volatilecomposition 24, as the lower porosity has a lower release rate, whereasthe higher porosity has a higher release rate. Having a higher porosityin one portion of the base material 12 (such as inner layer or innerply) compensates for the fact that the volatile composition 24 has totravel through more layers/plies to reach the outside of the basematerial 12. It is also noted that the density of the base material 12affects the internal reservoir of the base material 12 (i.e., thecapacity to absorb the volatile composition 24).

In some embodiments, different thicknesses of the base material 12 mayhave different amounts of compression applied during the manufacturingprocess such that the resultant base materials 12 may have varyingdensities, porosities, and absorbencies.

Additional description of base materials, porosity, pulp concentrations,etc. may be found in U.S. Publication No. 2011/0262377, the entirecontents of which is incorporated herein by reference.

In certain embodiments, the porosity of the pulp base material 12 may becontrolled such that the pulp base material 12 is configured withvarying porosity zones 1202. In some embodiments, the porosity zones1202 may be formed by changing the compactness of the fibers within thepulp base material 12.

For example, the pulp base material 12 may be formed within a mold 1204,as shown in FIG. 1. The mold 1204 is configured to form a pulp basematerial 12 having at least one high porosity zone 1206 and at least onelow porosity zone 1208.

The pulp base material 12 positioned over the portion of the mold 1204having a plurality of apertures 1209 in the base surface comprises thelow porosity zone 1208. When pressure is uniformly applied to the pulpbase material 12, more water is removed from that zone of the pulp basematerial 12 via the drainage apertures 1209. As a result, the lowporosity zone 1208 will have greater fiber compactness (and thus agreater density).

In contrast, the pulp base material 12 positioned over the portion ofthe mold 1204 with the solid base surface comprises the high porosityzone 1206. When pressure is uniformly applied to the pulp base material12, less water is removed from that zone of the pulp base material 12because there is no additional drainage mechanism to assist with waterremoval. As a result, the high porosity zone 1206 will have less fibercompactness (and thus a lower density).

As best illustrated in FIGS. 2-3, there may be transitional porosityzones 1210 between the high porosity zone 1206 and the low porosity zone1208, in which the fiber compactness gradually changes. When thevolatile composition(s) 24 are infused into zones 1206, 1208 of the pulpbase material 12, a certain amount of wicking of the volatilecomposition(s) 24 may occur through the transitional porosity zones1210.

In further embodiments, as best illustrated in FIGS. 4-9, a divider 1212may be positioned, or at least partially embedded within the pulp basematerial 12. To position the divider 1212 within the pulp base material12, the divider 1212 may be positioned within the mold 1204 when thepulp composition is introduced into the mold 1204. The divider 1212 maybe shaped to separate the zones 1206 and 1208 so as to eliminate some orsubstantially all of the transitional porosity zones 1210, as well assome or substantially all of the wicking of the volatile composition 24between the various porosity zones 1202.

In some embodiments, the pulp base material 12 with a lowerconcentration of pulp fibers may be added to the high porosity zone1206, and the pulp base material 12 with a higher concentration of pulpfibers may be added to the low porosity zone 1208. When pressure isuniformly applied to the mold 1204, the high porosity zone 1206 willhave less fiber compactness (and thus a lower density) than the lowporosity zone 1208. When pressure is applied to compact the mold 1204 toa uniform distance, the low porosity zone 1208 will have greater fibercompactness (and thus a higher density) due to a greater number offibers per volume, than the high porosity zone 1206.

Alternatively, a pulp base material 12 having a uniform concentration ofpulp fibers may be added to both zones 1206, 1208. More pressure may beapplied to the low porosity zone 1208, thereby compressing it more toreduce the porosity (i.e., by compacting the fibers more and increasingthe density). In contrast, less pressure may be applied to the highporosity zone 1206, thereby compressing it less than the low porosityzone 1208.

As best illustrated in FIGS. 5-6, the divider 1212 may be shaped so asto be at least partially embedded within the pulp base material 12. Inthese embodiments, a portion of the pulp base material 12 may extendover an upper (FIGS. 5-6) and/or lower (FIG. 6) surface of the divider1212 so that the divider 1212 is not visible through the overlappingpulp base material 12. When the volatile composition(s) 24 are infusedinto zones 1206, 1208 of the pulp base material 12, a certain amount ofwicking of the volatile composition(s) 24 may occur through theoverlapping pulp base material 12.

In other embodiments, as best illustrated in FIGS. 4 and 6-9, thedivider 1212 may be shaped so as to form at least a portion of a visiblesurface of the article 10. In these embodiments, the divider 1212 may beshaped so as to form a portion of a decorative design or otheraesthetically appealing surface treatment of the article 10.

In further embodiments, the porosity zones 1202 may be formed byintroducing varying amounts of a pore-forming agent such as a gas orgas-forming material. The gas or gas-forming material may be introducedinto the pulp base material 12 prior to or after introduction into themold 1204. Examples of gas-forming materials include solids, volatileliquids, chemical reagents, such as calcium carbonate and acid,thermally decomposable materials which will cause evolution of a gas by,for example, decomposition of bicarbonate, or biological agents, such asdextrose and yeast. Different amounts of gas or gas-forming materialsmay be introduced into each zone 1206, 1208, thereby producing zoneswith differing porosities, even if the fiber content of each zone isapproximately the same. For example, the high porosity zone 1206 may beinfused with a larger amount of a gas or gas-forming material, therebyhaving a greater porosity, while the low porosity zone 1208 may beinfused with a lesser amount of a gas or gas-forming material, therebyhaving a lower porosity.

In further embodiments, zones 1206 and 1208 may be formed in completelyseparate molds 1204 using any of the above techniques (i.e., fibercompactness, infusion of gas or gas-forming materials, refining,additives, or any other porosity-controlling method described above) toadjust the porosity of zone 1206 relative to the porosity of zone 1208.

Furthermore, as described in FIG. 10, the pulp base material 12 may beformed using at least two molding steps. In the first step, pulpcomposition is added to a first mold 1204A, which is then compressedusing a higher pressure (in the range of 0.1 lb/in² to 100 lb/in²) toform the low porosity zone 1208. The pulp base material 12 is removedfrom the first mold 1204A, and then inserted into a second mold 1204Bhaving a larger volume than the first mold 1204A. Additional pulpcomposition is then added to the second mold 1204B to surround the pulpbase material 12 from the first mold 1204A. The material inside mold1204B is then compressed using a lower pressure (in the range of 0.1lb/in² to 100 lb/in²) to form the high porosity zone 1206. Thistechnique forms a pulp base material 12 having discrete porosity zones1202 without the transitional porosity zones 1210 forming between theporosity zones 1202 and also without the need for a divider 1212 toseparate the zones. Additionally, a treatment may be applied to the lowporosity zone 1208 before additional pulp composition is added to thesecond mold 1204B to maintain the shape and/or density of the lowporosity zone 1208 after addition of the additional pulp composition.Examples of the treatment include, but are not limited to wet strengthagents, binders, wax, starch, sizing, cross-linking reagents, and/or anyother suitable agent.

In the embodiments where the divider 1212 is shaped so as to completelyeliminate any overlapping pulp base material 12 between the zones 1206,1208 and/or where the zones 1206, 1208 are formed in different molds,joining mechanisms 1214 between the zones 1206, 1208 may be used todiscrete units of the pulp base material 12 into the article 10, asillustrated in FIGS. 17-18, 30A, 31-32, and 40.

Examples of suitable joining mechanisms 1214 may include but are notlimited to any suitable chemical fasteners such as adhesives, coatings,wax, starch, and gums, and/or any suitable mechanical fasteners such asmale/female clips, anchors, hook and loop fasteners, pins, screw-typefasteners, impregnation-type fasteners, and magnets. These mechanicalfasteneres may, in certain embodiments, be part of the molding processitself and may be made out of pulp.

FIG. 17 illustrates an example of joining mechanisms 1214 that may beused. In certain embodiments, the joining mechanisms 1214 may beincluded in the mold when the pulp base material 12 is formed. In otherembodiments, the joining mechanisms 1214 may be added to the zones 1206,1208 after the molding process is completed.

While the above description of the pulp base material 12 focused on twoporosity zones 1206, 1208, the embodiments are by no means so limited.For example, the above techniques and mechanisms may be used to form apulp base material 12 having any suitable number of zones, including butnot limited to three, four, five, six, or more zones. As illustrated inFIG. 9, the pulp base material 12 may include eight zones: zones 1206Ahaving the highest porosity, 1206B having high porosity, 1208A havinglow porosity, and 1208B having the lowest porosity.

Furthermore, the zones may have any suitable shape, which includes butis not limited to wedge or pie shapes, rectilinear, elliptical,circular, or any suitable type of simple or complex geometry.Furthermore, while the zones 1206, 1208 have been described as beingformed with different porosities, the person of ordinary skill in therelevant art will understand that the zones 1206, 1208 may be formed ofthe same or similar porosities using any of the forming or joiningtechniques discussed above.

Furthermore, as best illustrated in FIGS. 2 11-12, 17-18, 30A, 31-32,and 40, the zones may be formed with a relatively smooth interlockingsurface 1216 for joining with other zones, while also having a veryrough or complex exterior-facing surface 1218 that may include manypeaks 1226 that form the outer surface of the pulp base material 12.

In some embodiments, the complex geometry of the exterior-facing surface1218 may provide additional release rate control. For example, as shownin the attached microphotographs in FIGS. 71 and 72, the pulp basematerial 12 contains mini-variations in pulp compositions that arelocated within peaks 1226 that are located on the surface 1218. Theshape of the peaks 1226 causes the pulp fibers to become more highlyconcentrated at a micro-scale in these areas, whereas the valleys orflatter regions 1228 are configured for better pulp fiber dispersion ata micro-scale. As a result, there are variations in release rates frompeak areas 1226 as compared to the flatter regions 1228. Additionally,as explained in more detail below, the different surface areas of thepeaks 1226 and the valleys or flatter regions 1228 will also providerelease rate control. Thus, the surface geometry may be configured toprovide more peaks 1226 within the zone 1206 to further enhance therelease rate of the “base notes,” while using a smoother surface texturewithin zone 1208 to further regulate the release rate of the “topnotes.” Thus, the release rate can be tailored by density and/or surfacearea differences.

The location and concentration of the peaks 1226 also enhances thedirectionality of the release of the volatile composition 24. Forexample, the peaks 1226 act as small three-dimensional emitters, thusallowing the volatile composition 24 to emit from the raised surface ofthe peak 1226 in all directions. In contrast, the flatter regions 1228tend to emit in more limited directionality because there is lesssurface area that faces in a range of directions. The range of emittingdirectionality provided by the peaks 1226 and flatter regions 1228 maybe optimized and tied with locations of certain volatile compositions 24within the pulp base material 12. The surface geometry may be designedto work in conjunction with porosity zones 1202 and/or with a pulp basematerial 12 having a relatively uniform porosity.

In some embodiments, as illustrated in FIGS. 20-26, 28-29, 30A-30B, 35,59-64, and 73-76, the article 10 may include an attachment element 1002for attaching the article 10 to another article or to other objects,such as a portion of any form of transportation (such as a cabin of acar, plane, train, boat, etc.), a Christmas tree or other real orartificial ornamentation or decoration, a fixture in a home or office,or a body. Such an attachment element 1002 may comprise a hole withinthe pulp base material 12 through which a hook, clip, loop, string,prongs, band, magnet, or other mechanisms for attaching an article to asurface, another article, or another structure may be inserted orotherwise coupled to the article 10. In other embodiments, the article10 may comprise an attachment element 1002 that is configured topenetrate through at least a portion of the pulp base material 12.

The attachment element 1002 may be formed in or attached to the article10 after the pulp base material 12 has been molded. The attachmentelement 1002 may also be connected to or formed as part of the divider1212 or other structure that is placed into the mold 1204 with the pulpcomposition so that the attachment element 1002 is at least partiallyembedded within the pulp base material 12.

In some embodiments, as best illustrated in FIGS. 11-12, 17-18, 24-25,31, the article 10 may include an externally-facing smooth surface 1220that forms a support surface to hold the article 10 in an uprightposition when positioned on another surface such as a table, desk,counter, window sill, etc.

In certain embodiments, as best illustrated in FIGS. 23, and 35-44, astand 1006 may be configured to couple to the article 10. The stand 1006may be formed of any material that does not absorb or transmit thevolatile composition 24 so as to prevent contact between the article 10and other surfaces. Suitable materials include, but are not limited tometal, metalized films, ceramic, glass, glazed ceramics, plastic,polymers, and any other impervious material.

In other embodiments, as best illustrated in FIGS. 8, 24-27, and 29, thearticle 10 may include a backing layer 1222 that is applied to at leastone surface of the article 10. The backing layer 1222 may be formed ofany material that does not absorb or transmit the volatile composition24 so as to prevent contact between the article 10 and other surfaces.Suitable materials include but are not limited to metal, metalizedfilms, ceramic, glass, glazed ceramics, plastic, polymers, and any otherimpervious material.

The backing layer 1222 may be applied to the article 10 after the pulpbase material 12 has been molded using any suitable chemical fastenerssuch as adhesives, coatings, wax, starch, gum and/or any suitablemechanical fasteners such as snap-fit design, male/female clips,anchors, hook and loop fasteners, pins, screw-type fasteners,impregnation-type fasteners, roughness or compatibility of the surfaceto bind pulp fibers, and magnets.

In certain embodiments, as best illustrated in FIG. 8, the backing layer1222 may also be connected to or formed as part of the divider 1212 orother structure that is placed into the mold 1204 with the pulpcomposition so that the backing layer 1222 forms an exterior surface ofthe base pulp material 12.

In further embodiments, as best illustrated in FIGS. 14-16, 21, 41 and43, the article 10 may further include a dowel or other opening 1224that extends through a portion of or entirely through the article 10.The opening 1224 may be formed within the pulp base material 12 duringthe molding process or may be formed in the article 10 using amechanical tool to form the opening 1224. The opening 1224 may beconfigured for placement of a light source, such as an light emittingdiode or other light source, within the article 10.

In further embodiments, one or more openings 1224 may form a receptaclefor the insertion of other pulp base materials 12 or other materials orobjects. For example, as best illustrated in FIGS. 15-16, the pulp basematerial 12 may be molded having a uniform first porosity withoutporosity zones 1202 but with at least one opening 1224. This opening1224 may be shaped to receive another pulp base material 12 that ismolded having a uniform second porosity without porosity zones 1202 andhaving a shape that substantially conforms to the shape and dimensionsof the opening 1224. Once the second pulp base material 12 is insertedinto the opening 1224, the article 10 may then comprise differentporosity zones 1202 resulting from the different porosities of the otherpulp base materials 12. Additional openings 1224 may be included withthe article 10, and more pulp base materials 12 with additionaldifferent porosities may be inserted to form a plurality of porosityzones 1202. In further embodiments, other items such as scented rods ofspiral wound paper, may be inserted into the openings 1224. Thus, theopenings 1224 may serve as a way to replenish the volatile composition24 within the article 10 by removing older base materials 12 or scentedrods from which the scent has been depleted, and replacing them with newones.

In other embodiments, as best illustrated in FIG. 19, a capillarystructure 1230 may be incorporated into the dividers 1212 and/or may bea separate structure that is added to the mold 1204 prior to or duringthe pulp composition addition. This capillary structure 1230 maycomprise a length of tubing 1232 having one open end 1234 accessiblefrom an outer surface of the pulp base material 12 and an opposing end1236 terminating within the body of the pulp base material 12. Theopposing end 1236 may be connected to the divider 1212 to suspend thecapillary structure 1230 within the mold 1204 during the pulpcomposition addition and molding process.

In certain embodiments, the capillary structure 1230 may compriseseparate tubing extending through each zone 1206, 1208. The tubing mayfurther comprise a series of small apertures 1238 along its length. Thecapillary structure 1230 may be used to reintroduce a volatilecomposition 24 into the zones 1206, 1208 once the concentration isdepleted. The volatile composition 24 is introduced through the open end1234 and disperses into the zones 1206, 1208 via the apertures 1238.Each zone 1206, 1208 may receive a different volatile composition 24and/or the re-fill design allows for the volatile compositions 24 to bereplaced with different scents as desired.

In certain embodiments, as best illustrated in FIGS. 45-46, 48-49, and51-58, the article 10 may be combined with at least one energy source1004, including but not limited to a heating element (such as a warmerbowl or plate, electrical plug-in, chemical warmer pack, candle, lightsource, heating element system, and any other heat generating object)and a wind element (such as a fan, blower, air circulation vent,bladeless fan, and any other air movement object).

The article 10 may be combined with the energy source 1004 in a varietyof manners. A variety of energy sources that are attached and/or placedin close proximity to articles containing volatile compositions aredescribed in U.S. Publication No. 2015/0217016, the entire contents ofwhich is incorporated herein by reference.

In some embodiments, the article 10 may be positioned within a warmerbowl or plate 1004, wherein the article 10 is heated through contactwith the surface of the warmer bowl 1004. The surface of the warmer bowlor plate 1004 produces heat in a range of approximately 90° F. to 250°F. In further embodiments, a chemical warmer pack 1004 may be attachedor positioned adjacent to the article 10.

In these embodiments, the backing layer 1222 may be configured to serveas a contact surface between the article 10 and the warmer bowl 1004. Toimprove the efficiency of heat transfer between the article 10 and thewarmer bowl 1004, the backing layer 1222 may be formed of a conductivematerial such as tin, copper, aluminum, or other suitable metallicmaterials.

According to some embodiments, the article 10 may be shaped into a lightshade or screen, which is positioned around and/or near an incandescentlight bulb. For example, the article 10 may be positioned as a screenfor a night light or a shade for small decorative lights. The article 10may also be configured as a lamp shade or screen for larger bulbs.

The article 10 may also be positioned within the path of and/or coupledto a wind element such as a fan, as shown in FIGS. 57-58 and 77-78B. Insome embodiments, the article 10 may form at least a portion of one ormore blades of the fan and/or may be attached to a vent cover. In theseembodiments, the article 10 may be positioned within a support structure1008, such as the pronged structure 1008 shown in FIGS. 59-64 or the cupstructure 1008 in FIGS. 77-78B. Prongs 1010 extend to partially enclosesides of the article 10 to secure the article 10 to the supportstructure 1008. The prongs 1010 may be attached to the support structure1008 (as shown in FIGS. 59-64) or to the decorative cover 1012 (as shownin FIGS. 77-78B). The support structure 1008 also comprises anattachment element 1002, which secures the support structure 1008 to avent blade or other suitable surface. In some embodiments, as shown inFIG. 78B, the attachment element 1002 may include a pair of clampmembers biased toward one another that can engage a suitable surface,such as an exterior portion of a fan or a vent in an automobile. Thesupport structure 1008 may further comprise a decorative cover 1012 thatattaches to an outer surface of the prongs 1010.

The heat generated by the energy source 1004 heats the volatilecomposition 24 within the article 10 so as to facilitate its release,and the wind generated by the energy source 1004 creates an air flowover the article 10, which facilitates dispersion of the volatilecomposition 24.

As shown in FIGS. 73-76, the article 10 may include a plurality of zoneswith different densities. The article 10 may have any number of zoneswith different respective densities. For example, the article 10 mayinclude a first density zone 1241, a second density zone 1242, a thirddensity zone 1243, and a fourth density zone 1244. In some embodiments,the density zones may correlate to various porosity zones, as describedabove (e.g., high porosity zones 1206 and low porosity zones 1208). Insome cases, a high density zone correlates to a low porosity zone 1208and a low density zone correlates to a high porosity zone 1206. However,the article 10 is not limited to two density/porosity zones and may haveany number of density/porosity zones. In addition to affecting theabsorption and subsequent release of the volatile composition 24(explained in greater detail below), the various density zones may alsoaffect the aesthetics/appearance of article 10. In some embodiments, thevolatile composition 24 may be combined with a dye (such as an oilsoluble dye). Various dyes are described in greater detail below. Thecolor of the dye in the volatile composition 24 appears more dark orconcentrated in the high density areas of article 10. In some cases, thebase material 12 is approximately white and the dye is a color (such asred, blue, green, etc.) such that the lower density areas appear closerto the white color of the base material 12 while the higher densityareas have a darker color closer to the color of the dye.

FIGS. 73 and 74 show an example of an article 10 formed in the shape ofan angel (see also FIGS. 24-28, 34, 35, 37, 40). In some embodiments,the second density zone 1242 corresponds to the wings of the angel andhas the highest density of the article 10. The first and third densityzones 1241 and 1243 shown in FIGS. 73 and 74 have lower densities thanthe second density zone 1242. In some embodiments, the face/head of theangel (first density zone 1241) has a low density and the dress/body ofthe angel (third density zone 1243) has a moderate density that isgreater than the density of the first density zone 1241 but less thanthe density of the second density zone 1242.

In some embodiments, the first density zone 1241 is approximately 0.6g/cm³ to 0.9 g/cm³ and the second density zone 1242 is approximately 1.0g/cm³ to 1.2 g/cm³. In certain embodiments, the first density zone 1241is approximately 0.7 g/cm³ to 0.75 g/cm³ and the second density zone1242 is approximately 1.05 g/cm³ to 1.1 g/cm³. As the density of article10 increases, the maximum amount of fragrance (liquid, such as volatilecomposition 24) that can be absorbed into article 10 decreases. In someembodiments, after liquid has been absorbed, the first density zone 1241has a percent fragrance load of approximately 50%-54% and the seconddensity zone 1242 has a percent fragrance load of approximately 42%-46%.In certain embodiments, after liquid has been absorbed, the firstdensity zone 1241 has a percent fragrance load of approximately51.5%-52.5% and the second density zone 1242 has a percent fragranceload of approximately 43.5%-44.5%.

FIGS. 75 and 76 show examples of an article 10 formed in the shape of asnowflake (see also FIG. 50). These figures show two versions of thearticle 10, version (a) and version (b) where version (b) has aheight/thickness h₂ that is larger than the height h₁ of version (a). Insome embodiments, h₂ is approximately 50% larger than h₁. In someexamples, h₂ is approximately 1.5 mm and h₁ is approximately 1 mm.Version (a) has a first density zone 1241 and a second density zone 1242where the second density zone 1242 has a higher density than the firstdensity zone 1241. Version (b) has a third density zone 1243 and afourth density zone 1244 where the fourth density zone 1244 has a higherdensity than the third density zone 1243. The increased height/thicknessof version (b) dictates that the third density zone 1243 has a lowerdensity than the first density zone 1241 of version (a), which allowsfor better color contrast between third density zone 1243 and fourthdensity zone 1244 (compared to the contrast between first density zone1241 and second density zone 1242).

The article 10 may also include a channel 1250 on the rear side (seeFIGS. 74 and 76). The shape of the channel 1250 may approximately matchthe perimeter of the article 10 (as shown in FIGS. 74 and 76 with anoffset from the perimeter on the rear side of the article 10), althoughthis is not necessary. In some embodiments, during the manufacturingprocess of the article 10, a specific amount of volatile composition 24(or a combination of volatile composition 24 and an oil soluble dye) maybe poured into the channel 1250. As shown in FIG. 74, the channel 1250may include at least one auxiliary channel 1251, 1252. The auxiliarychannels 1251, 1252 may ensure liquid poured into the channelaccumulates in specific regions and/or may reduce overall thickness ofthe article 10 in specific areas. Reducing a local thickness of thearticle 10 increases the compression in the local area thus increasingdensity of the article 10 at the desired location, which allows forgreater detail surface detail to be molded at the exterior-facingsurface 1218. For example, the first auxiliary channel 1251 may belocated opposite of the face of the angel thus allowing facial features(e.g., mouth, eyes, etc.) to be molded into the exterior-facing surface1218 (see FIGS. 73 and 74). Similarly, the second auxiliary channel 1252may be located opposite of the dress of the angel thus allowing features(e.g., stripes, etc.) to be molded into the exterior-facing surface 1218(see FIGS. 73 and 74). In some embodiments, the first auxiliary channel1251 may have an approximately circular (2D) or partially spherical (3D)shape. In certain embodiments, the second auxiliary channel 1252 mayhave an approximately triangular (2D) or partially conical (3D) shape.The article 10 may also be submerged into a container of volatilecomposition 24 (or a combination of volatile composition 24 and an oilsoluble dye). One or both of the pouring of the volatile composition 24into the channel or submerging the article 10 into the container may becompleted by a robotic device.

As described above, the density of the article 10 affects the amount ofliquid fragrance that can be absorbed. In some embodiments, after thevolatile composition 24 (or the combination of volatile composition 24and the oil soluble dye) is added, the overall articles 10 shown inFIGS. 73-76 are approximately 30%-60% liquid (by weight). Some examplesof the articles 10 may have 40% liquid by weight while other articles 10may have 50% liquid by weight. In some embodiments, the article 10 hasan internal reservoir capable of receiving up to 5-15 g of volatilecomposition 24 (or the combination of volatile composition 24 and theoil soluble dye). In some embodiments, the internal reservoir of thearticle 10 is capable of receiving up to 9 g of volatile composition 24(i.e., the maximum liquid capacity). In some embodiments, the article 10is designed to absorb approximately ⅔ of maximum liquid capacity. Insome embodiments, the article 10 is designed to absorb approximately 6 gof volatile composition 24.

The channel 1250 may be designed such that the volume of the channel1250 approximately corresponds to the maximum liquid capacity of thearticle 10. In some cases, the volume of the channel 1250 approximatelycorresponds to the desired amount of liquid to be absorbed by thearticle 10 during the manufacturing process, while in other embodiments,the volume of the channel 1250 is less than the desired amount of liquidto be absorbed by the article 10 during the manufacturing process basedon the assumption that absorption begins immediately when liquid ispoured into the channel.

B. Volatile Composition

The volatile composition 24 may include, but is not limited tofragrances, flavor compounds, odor-eliminating compounds, aromatherapycompounds, natural oils, water-based scents, odor neutralizingcompounds, and outdoor products (e.g., insect repellent).

As used herein, “volatile substance” refers to any compound, mixture, orsuspension of compounds that are odorous, or any compound, mixture, orsuspension of compounds that cancel or neutralize odorous compounds,such as any compound or combination of compounds that would produce apositive or negative olfactory sense response in a living being that iscapable of responding to olfactory compounds, or that reduces oreliminates such olfactory responses.

A volatile composition as used herein comprises one or more volatilesubstances, and is generally a composition that has a smell or odor,which may be volatile, which may be transported to the olfactory systemof a human or animal, and is generally provided in a sufficiently highconcentration so that it will interact with one or more olfactoryreceptors.

A fragrance may comprise an aroma or odorous compound, mixture orsuspension of compounds that is capable of producing an olfactoryresponse in a living being capable of responding to olfactory compounds,and may be referred to herein as odorant, aroma, or fragrance. Afragrance composition may include one or more than one of the fragrancecharacteristics, including top notes, mid notes or heart, and dry downor base notes. The volatile composition 24 may comprise other diluentsor additives, such as solvents or preservatives.

Examples of volatile compositions 24 useful in the present inventioninclude, but are not limited to esters, terpenes, cyclic terpenes,phenolics, which are also referred to as aromatics, amines and alcohols.Further examples include, but are not limited to furaneol 1-hexanol,cis-3-Hexen-1-ol, menthol, acetaldehyde, hexanal, cis-3-hexenal,furfural, fructone, hexyl acetate, ethyl methylphenylglycidate,dihydrojasmone, wine lactone, oct-1-en-3-one, 2-Acetyl-1-pyrroline,6-acetyl-2,3,4,5-tetrahydropyridine, gamma-decalactone,gamma-nonalactone, delta-octalactone, jasmine, massoia lactone, sotolonethanethiol, grapefruit mercaptan, methanethiol,2-methyl-2-propanethiol, methylphosphine, dimethylphosphine, methylformate, nerolin tetrahydrothiophene, 2,4,6-trichloroanisole,substituted pyrazines, methyl acetate, methyl butyrate, methylbutanoate, ethyl acetate, ethyl butyrate, ethyl butanoate, isoamylacetate, pentyl butyrate, pentyl butanoate, pentyl pentanoate, isoamylacetate, octyl acetate, myrcene, geraniol, nerol, citral, lemonal,geranial, neral, citronellal, citronellol, linalool, nerolidol,limonene, camphor, terpineol, alpha-ionone, terpineol, thujone,benzaldehyde, eugenol, cinnamaldehyde, ethyl maltol, vanillin, anisole,anethole, estragole, thymoltrimethylamine, putrescine, diaminobutane,cadaverine, pyridine, indole and skatole. Most of these are organiccompounds and are readily soluble in organic solvents, such as alcoholsor oils. Fragrance includes pure fragrances, such as those includingessential oils, and are known to those skilled in the art. Water-basedodorous compounds and other odorous compositions are also contemplatedby the present invention.

Fragrance oils as olfactory-active compounds or compositions usuallycomprise many different perfume raw materials. Each perfume raw materialused differs from another by several important properties includingindividual character and volatility. By bearing in mind these differentproperties, and others, perfume raw materials may be blended to developa fragrance oil with an overall specific character profile. To date,characters are designed to alter and develop with time as the differentperfume raw materials evaporate from the substrate and are detected bythe user. For example, perfume raw materials which have a highvolatility and low substantivity are commonly used to give an initialburst of characters such as light, fresh, fruity, citrus, green, ordelicate floral to the fragrance oil, which are detected soon afterapplication. Such materials are commonly referred to in the field offragrances as “top notes.” By way of a contrast, the less volatile, andmore substantive, perfume raw materials are typically used to givecharacters such as musk, sweet, balsamic, spicy, woody or heavy floralto the fragrance oil, which may also be detected soon after application,but also last far longer. These materials are commonly referred to as“middle notes” or “base notes.” Highly skilled perfumers are usuallyemployed to carefully blend perfume raw materials so that the resultantfragrance oils have the desired overall fragrance character profile. Thedesired overall character is dependent both upon the type of compositionin which the fragrance oil will finally be used and also the consumerpreference for a fragrance.

In addition to the volatility, another important characteristic of aperfume raw material is its olfactory detection level, otherwise knownas the odor detection threshold (ODT). If a perfume raw material has alow odor detection threshold, only very low levels are required in thegas phase, or air, for it to be detected by the human, sometimes as lowas a few parts per billion. Conversely, if a perfume raw material has ahigh ODT, larger amounts or higher concentrations in the air of thatmaterial are required before it can be smelled by the user. The impactof a material is its function of its gas phase or air concentration andits ODT. Thus, volatile materials, capable of delivering large gas-phaseconcentrations, which also have low ODTs, are considered to beimpactful. To date, when developing a fragrance oil, it has beenimportant to balance the fragrance with both low and high volatility rawmaterials, as the use of too many high volatility materials may lead toa short lived, overwhelming scent. As such, the levels of high odorimpact perfume raw materials within a fragrance oil have traditionallybeen restricted.

As used herein, the term “fragrance oil” relates to a perfume rawmaterial, or mixture of perfume raw materials, that are used to impartan overall pleasant odor profile to a composition, preferably a cosmeticcomposition. As used herein, the term “perfume raw material” relates toany chemical compound which is odorous when in an un-entrapped state.For example, in the case of pro-perfumes, the perfume component isconsidered to be a perfume raw material, and the pro-chemistry anchor isconsidered to be the entrapment material. In addition, “perfume rawmaterials” are defined by materials with a ClogP value preferablygreater than about 0.1, more preferably greater than about 0.5, evenmore preferably greater than about 1.0. As used herein the term “ClogP”means the logarithm to base 10 of the octanol/water partitioncoefficient. This can be readily calculated from a program called“CLOGP,” which is available from Daylight Chemical Information SystemsInc., Irvine Calif., USA. Octanol/water partition coefficients aredescribed in more detail in U.S. Pat. No. 5,578,563.

Examples of residual “middle and base note” perfume raw materialsinclude, but are not limited to ethyl methyl phenyl glycidate, ethylvanillin, heliotropin, indol, methyl anthranilate, vanillin, amylsalicylate, coumarin. Further examples of residual perfume raw materialsinclude, but are not limited to, ambrox, bacdanol, benzyl salicylate,butyl anthranilate, cetalox, ebanol, cis-3-hexenyl salicylate, lilial,gamma undecalactone, gamma dodecalactone, gamma decalactone, calone,cymal, dihydro iso jasmonate, iso eugenol, lyral, methyl beta naphthylketone, beta naphthol methyl ether, para hydroxylphenyl butanone,8-cyclohexadecen-1-one, oxocyclohexadecen-2-one/habanolide, florhydral,intreleven aldehyde.

Examples of volatile “top note” perfume raw materials include, but arenot limited to anethol, methyl heptine carbonate, ethyl aceto acetate,para cymene, nerol, decyl aldehyde, para cresol, methyl phenyl carbinylacetate, ionone alpha, ionone beta, undecylenic aldehyde, undecylaldehyde, 2,6-nonadienal, nonyl aldehyde, octyl aldehyde. Furtherexamples of volatile perfume raw materials include, but are not limitedto phenyl acetaldehyde, anisic aldehyde, benzyl acetone, ethyl-2-methylbutyrate, damascenone, damascone alpha, damascone beta, flor acetate,frutene, fructone, herbavert, iso cyclo citral, methyl isobutenyltetrahydro pyran, isopropyl quinoline, 2,6-nonadien-1-ol,2-methoxy-3-(2-methylpropyl)-pyrazine, methyl octine carbonate,tridecene-2-nitrile, allyl amyl glycolate, cyclogalbanate, cyclal C,melonal, gamma nonalactone, c is 1,3-oxathiane-2-methyl-4-propyl.

Other useful residual “middle and base note” perfume raw materialsinclude, but are not limited to eugenol, amyl cinnamic aldehyde, hexylcinnamic aldehyde, hexyl salicylate, methyl dihydro jasmonate,sandalore, veloutone, undecavertol, exaltolide/cyclopentadecanolide,zingerone, methyl cedrylone, sandela, dimethyl benzyl carbinyl butyrate,dimethyl benzyl carbinyl isobutyrate, triethyl citrate, cashmeran,phenoxy ethyl isobutyrate, iso eugenol acetate, helional, iso E super,ionone gamma methyl, pentalide, galaxolide, phenoxy ethyl propionate.

Other volatile “top note” perfume raw materials include, but are notlimited to benzaldehyde, benzyl acetate, camphor, carvone, borneol,bornyl acetate, decyl alcohol, eucalyptol, linalool, hexyl acetate,iso-amyl acetate, thymol, carvacrol, limonene, menthol, iso-amylalcohol, phenyl ethyl alcohol, alpha pinene, alpha terpineol,citronellol, alpha thuj one, benzyl alcohol, beta gamma hexenol,dimethyl benzyl carbinol, phenyl ethyl dimethyl carbinol, adoxal, ally!cyclohexane propionate, beta pinene, citral, citronellyl acetate,citronellal nitrile, dihydro myrcenol, geraniol, geranyl acetate,geranyl nitrile, hydroquinone dimethyl ether, hydroxycitronellal,linalyl acetate, phenyl acetaldehyde dimethyl acetal, phenyl propylalcohol, prenyl acetate, triplal, tetrahydrolinalool, verdox,cis-3-hexenyl acetate.

In certain embodiments, the volatile composition 24 may comprise afragrance component having a release rate ranging from 0.001 g/day to2.0 g/day. The formulation of the fragrance may comprise any suitablecombination of top, mid, and base note components.

In certain embodiments, the pulp base material 12 may be infused withmore than one volatile composition 24 that is paired with a suitablezone 1206, 1208 within the pulp base material 12 to achieve a blendedrelease rate designed to optimize the “top note” and “middle and basenote” release rates.

As discussed above, the porosity (which may be controlled by fibercompactness, infusion of gas or gas-forming materials, refining,additives, or any other porosity-controlling method described above) mayaffect the uptake or load amount of the volatile composition 24, or mayaffect the rate of release of the volatile composition 24. For example,high porosity zone 1206, which has a lower fiber compactness, willprovide an easier release of the volatile composition 24 because thereare larger air passages between the fibers. Thus, a volatile composition24 comprising mostly “middle and base note” components may beincorporated into the high porosity zone 1206 to provide an earlierrelease of the “middle and base note” components.

In contrast, low porosity zone 1208, which has a higher fibercompactness, will provide a more controlled release of the volatilecomposition 24 because the network of air passages through the fibers istighter and more complex. Thus, a volatile composition 24 comprisingmostly “top note” components may be incorporated into the low porosityzone 1208 to provide a slower release of the “top note” components.

In other words, the pulp base material 12 may be engineered with aplurality of zones, each zone having a uniquely designed pulp porositythat correlates to the desired release rate of the particular noteswithin the different volatile compositions 24.

In some embodiments, the design may be to create a simultaneous andsustained release of all notes, which may be optimized by pairing “topnotes” with lower porosity zones, “middle notes” with medium porosityzones, and “base notes” with higher porosity zones.

In other embodiments, the design may be to create a staggered release ofdifferent scents over time, which may be optimized by reversing thepairing described above. In other words, the pulp base material 12 mayinclude a pairing of “top notes” with higher porosity zones 1202,“middle notes” with medium porosity zones 1202, and “base notes” withlower porosity zones 1202.

The test results described in Example 2 demonstrate that a pulp basematerial 12 having a density of 0.36 g/mL generates a different releaseprofile of a volatile composition with high and low molecular weightcompounds, when compared to a pulp base material 12 having a density of0.24 g/mL. In the fragrance industry, high molecular weight compoundsare categorized as “base note” compounds, and low molecular weightcompounds are categorized as “top note” volatile compounds.

Specifically, for samples containing only “base note” compound methylcedryl ketone (“MCK”) volatile composition 24, the lower density pulpbase material samples released approximately 12 times more “base note”MCK than the higher density pulp base material samples.

For samples containing both “top note” compound ethyl acetate volatilecomposition 24 and “base note” compound methyl cedryl ketone (“MCK”)volatile composition 24, the lower density pulp base material samplesand the higher density pulp base material samples released the “basenote” MCK at similar rates, while the lower density pulp base materialsamples released approximately 15 times more “top note” ethyl acetatethan the higher density pulp base material samples.

Finally, the lower density pulp base material samples showed a fasterrelease rate for all volatile compositions 24 over the higher densitypulp base material samples.

FIG. 79 shows weight loss data for first density zone 1241 and seconddensity zone 1242. In some embodiments, the data shown in FIG. 79 isrelevant to the embodiments shown in FIGS. 73 and 74. However, the datashown in FIG. 79 may be relevant to multiple embodiments. Because, asdescribed above, first density zone 1241 has a lower density (higherporosity) and thus can absorb more liquid compared to the second densityzone 1242, the first density zone 1241 exhibits a greater weight loss(per surface area). FIG. 79 also illustrates that the rate of the weightloss for second density zone 1242 reduces faster than the rate of theweight loss for first density zone 1241. FIG. 80 shows an example of thecumulative weight loss for an article 10 over a 21 day period. In someembodiments, the data shown in FIG. 80 is relevant to the embodimentsshown in FIGS. 73 and 74. However, the data shown in FIG. 80 may berelevant to multiple embodiments.

EXAMPLES Example 1. Synthesis of Pulp Matrix

Pulp material (15 g; southern hardwood; Sulfatate-H-J grade; RayonierPerformance Fibers, LLC) was added to a blender cup. A solutioncontaining (i) colloidal silica (5 g; Snowtex®-O (silica 20% wt/wt inwater); Nissan Chemical America Corporation), (ii) starch (5 g; MaltrinQD® M500 Maltodextrin NF; Grain Processing Corporation), (iii) bakingpowder (1 g; Clabber Girl Corporation), and (iv) water (221.5 g) wasadded to the blender cup. The content in the blender cup was blended toform a consistent pulp slurry, followed by removal of 100 g of excesssolution. The final pulp slurry was added to a silicone mold, where theshape of the mold is a cylinder with dimensions 1.8 cm diameter, 1.3 cmheight (volume: 3.31 cm³). The amount of pulp slurry used to create avarying density pulp cylinder is provided in Table 1.

TABLE 1 Pulp mass and density of pulp cylinder matrix Pulp slurry massDensity (g) Pulp dry mass (g) (g pulp/cm³) High density pulp 10 1.2 0.36cylinder Low density pulp 6 0.8 0.24 cylinder

Example 2. Headspace Gas Chromatography/Mass Spectrometry (GC/MS)Valuation of Release of High and Low MW Ingredients from a Pulp Matrix

The amount of release of a top note or base note volatile ingredientfrom the pulp matrix was evaluated using the standard method ASTMD4526-12 Standard for Determination of Volatiles in Polymers by StaticHeadspace Gas Chromatography. Headspace GC/MS experiments were carriedout on Agilent instruments: headspace model 7697A, GC model 7850A, andMS model 5975C. The top note and base note ingredients selected arecommon ingredients used in all types of olfactive compositions in thefragrance industry. Ethyl acetate (CAS 141-78-6; MW 88.1 g/mol) is thetop note ingredient that was tested, and methyl cedryl ketone (CAS32388-5-9; MW 246.4 g/mol) is the base note ingredient that was tested.The base note ingredient represents the high end of the molecular weightspectrum for volatile ingredients, and the top note ingredientrepresents the low end of the molecular weight spectrum for volatileingredients.

TABLE 2 Headspace GC/MS results demonstrating impact of packing densityin pulp base material 12 on release profile of olfactive volatilecompositions. Pulp Amount Amount matrix Compound GC/MS GC/MS EA MCKdensity injected peak area peak area detected detected Sample (g/mL) (7μL each) (EA) (MCK) (%) (%) EA NA EA 1191399736 NA 100 NA control MCK NAMCK NA 1437276114 NA 100 control 1 0.36 EA Below limit NA not detectedNA 2 0.36 MCK NA 21830631 NA 1.52 3 0.36 EA/MCK Below limit 3915890 notdetected 0.27 4 0.24 EA Below limit NA not detected 5 0.24 MCK NA270003206 NA 18.79 6 0.24 EA/MCK  186196145 4025104 15.63 0.28 EA =ethyl acetate; MCK = methyl cedryl ketone; NA = not applicable

Example 3. Illustration of Fiber Density in Pulp Base Material 12 byEpoxy Embedding and Thin Section Imaging

Samples of a three-dimensional pulp object with a high density (0.36g/mL) and a three-dimensional pulp object with a low density (0.24 g/mL)pulp base material 12 were analyzed using Epoxy Embedding and ThinSection Imaging. Each sample was vacuum filled with Epofix cold mountepoxy resin distributed by Electron Microscopy Sciences. A thin sectionof each sample was cut with a saw blade and immersed in Cargillrefractive index liquid (R.I.=1.572, which matches the R.I. of Epofix).Transmitted light imaging was then used to capture micrographs of thecross-sections of each sample, as may be seen in FIGS. 66, 67 and 68.The dark, spiked features at the centers of the samples indicateincomplete impregnation of the epoxy resin, which also indirectlyindicates fiber density. For example, as may be seen in FIG. 67, theepoxy resin impregnation is less complete in the high density samplethan in the low density sample shown in FIG. 66. Moreover, FIG. 68,which includes a sample of a three-dimensional pulp object with bothhigh density and low density pulp base material 12, also illustratesless complete epoxy resin impregnation in the area with a higher densitythan in the area with a lower density. Additionally, in FIG. 67, thefaint, gradual change in density from top to bottom in the high densitysample, excluding the dark center, is an artifact caused by a change inthin section thickness, as the sample is wedge-shaped. However, thesample in FIG. 68, which includes both high density and low density pulpbase materials 12, has a uniform thickness, and thus the faintly darkerupper half is indicative of the higher density pulp base material 12 inthat area.

C. Modulating Coating

As used herein, “coating” refers to any composition that may be appliedusing any suitable method to at least one of an outer surface of thearticle 10, to some or all surfaces of the pulp base material 12, and/ormay be uniformly or non-uniformly distributed throughout the internalstructure 20 of the base material 12 and/or the article 10. In cases ofsurface application, the coating may be applied so that the compositionmay or may not penetrate to at least some degree within the article 10and/or the base material 12.

Modulating coating 14 may be applied to at least one outer surface 16 ofthe base material 12 and/or to the article 10, and may be applied beforeor after loading of the volatile composition 24. In certain embodiments,the modulating coating 14 may penetrate into the internal structure 20of the base material 12 to a certain level, which may vary depending onthe porosity, processing methods, or other characteristics of the basematerial 12.

The modulating coating 14 is designed to slow the release rate of thevolatile composition 24 loaded into the internal structure 20 at higherconcentration levels and accelerate the release rate of the volatilecomposition 24 at lower concentration levels in order to achieve arelatively steady release of volatile composition 24 over time.

To explain the way that the modulating coating 14 works to have this“hold/push” effect over a range of load levels of the volatilecomposition 24, it is necessary to explain the way in which the releaserate of the volatile composition 24 is generated. The volatilecomposition 24 is loaded or absorbed into the internal structure 20 viathe pores 22 until a sufficiently high load level is achieved within theinternal structure 20 through various embodiments of loading methods,which are explained in detail below. The volatile composition 24 may beloaded or absorbed into the internal structure 20 before or after themodulating coating 14 is applied.

The initially high load level of the volatile composition 24 within theinternal structure 20 creates an internal force that causes the volatilecomposition 24 to diffuse or evaporate out of the internal structure 20as quickly as possible to a region of lower concentration. As the loadlevel of the volatile composition 24 decreases over time, the force thatcauses the diffusion or evaporation diminishes until there is no longera force remaining (i.e., an equilibrium point is reached where thevolatile composition 24 no longer diffuses or evaporates out of theinternal structure 20). The equilibrium point is usually higher than 0%concentration, which causes some of the volatile composition 24 tobecome trapped within the pores 22 of the internal structure 20.

In conventional applications, such as in U.S. Publication No.2011/0262377, a coating may be applied to form a layer that slows orretards the rapid release of a volatile composition at higherconcentration levels. These conventional coatings typically includesubstances that trap some of the volatile composition within the coatinglayer, which slows down the rate of release through the coating.However, because the coating only serves as a barrier or “speed bump” toslow down the rate of release of the volatile composition, the releasewill eventually stop once the concentration of volatile compositionwithin the internal structure reaches equilibrium (i.e., a level wherethere is no longer a sufficient concentration to drive the volatilecomposition through the coating layer, thus allowing some of volatilecomposition to remain trapped within the coating layer and/or within theinternal structure).

The modulating coating 14 comprises both a barrier substance 26 and ahygroscopic substance 28. In particular, in most embodiments, themodulating coating 14 comprises substances that do not chemicallyinteract with the volatile composition 24 itself

In these embodiments, when the modulating coating 14 is applied to theouter surface 16 of the internal structure 20, at the higherconcentration levels of the volatile composition 24 within the internalstructure 20, the barrier substance 26 forms a barrier or “speed bump”to slow down the rate of release of the volatile composition 24 throughthe modulating coating 14. At these higher initial concentration levels,as illustrated in the early stage section of FIG. 65, the hygroscopicsubstance 28 does not play a role in modulating the release rate of thevolatile composition 24 (i.e., does not absorb any water into themodulating coating 14) because the concentration of the volatilecomposition 24 within the internal structure 20 is sufficiently high toforce a certain amount of the volatile composition 24 to release throughthe modulating coating 14 at a rate that effectively blocks any waterfrom being attracted into the modulating coating 14 by the hygroscopicsubstance 28.

As the concentration level of the volatile composition 24 within theinternal structure 20 slowly diminishes, as illustrated in the mid stagesection of FIG. 65, the concentration of the volatile composition 24within the internal structure 20 is still sufficiently high to continueto force some of the volatile composition 24 out of the modulatingcoating 14 at a reduced rate of release.

One hypothesis to explain the phenomenon observed in the late stage isthat because there is a lower volume of the volatile composition 24exiting the modulating coating 14, the hygroscopic substance 28 beginsto attract more water (typically in the form of water vapor) into themodulating coating 14, whereupon the water adsorbs or absorbs to thehygroscopic substance 28 and begins to displace the volatile composition24 that is trapped by the barrier substance 26 within the modulatingcoating 14. This hypothesis is illustrated in the late stage section ofFIG. 65, and is based on known physical properties of the hygroscopicsubstance 28 and the data showing higher release rates at the end of theproduct life cycle, as compared to the same product without themodulating coating 14. Once displaced, the volatile composition 24 isreleased from the modulating coating 14, thereby creating an aggregaterate of release of the volatile composition 24 that may approximate therate of release driven by the higher load level of the volatilecomposition 24 alone.

As the load level of volatile composition 24 continues to drop to alevel that can no longer drive the volatile composition 24 out of themodulating coating 14, the hygroscopic substance 28 continues to pullmore and more water into the modulating coating 14. That water continuesto displace the trapped volatile composition 24, effectively forcing thedisplaced volatile composition 24 to be released from the modulatingcoating 14. For a period of time in the late stage, the rate of releaseof the volatile composition 24 due to water displacement driven by thehygroscopic substance 28 may approximate the rate of release driven bythe higher load level of the volatile composition 24 alone and/or mayapproximate the aggregate rate of release driven by both the higher loadlevel of the volatile composition 24 and water displacement driven bythe hygroscopic substance 28. As a result, where conventional coatingsthat contain only barrier substances 26 may have stopped releasingvolatile compositions once the equilibrium point of the concentration isreached within the internal structure 20, the modulating coating 14continues to provide a relatively constant release of the volatilecomposition 24.

An alternate hypothesis to explain the phenomenon observed in the latestage is that the water that is brought into the modulating coating 14by the hygroscopic substance 28 may act to degrade the barrier substance26, which would also allow for release of the volatile composition 24trapped within the modulating coating 14 and within the internalstructure 20 of the base material 12.

In any event, the test results demonstrate that the modulating coating14 generates an improved release profile of the volatile composition 24over the aromatic life cycle of the article 10, depending on theporosity of the internal structure 20 of the base material 12 and thevolatility levels of the volatile composition 24. Eventually, theconcentration of the volatile composition 24 within the internalstructure 20 and the amount trapped by the barrier substances 26 withinthe modulating coating 14 will reach such a low point that the amount ofvolatile composition 24 released on a daily basis by the modulatingcoating 14 will eventually decline to zero. A series of examplessupporting and explaining this process are provided in U.S. PublicationNo. 2016/0089468, the entire contents of which are incorporated hereinby reference.

In certain embodiments, the barrier substance 26 may comprisemaltodextrin (e.g. Maltrin). In other embodiments, the barrier substance26 may include, but is not limited to other dextrins, other film-formingpolysaccharides, other carbohydrates (mono-, di-, tri-, etc.), naturalunmodified starch, modified starch, any starch appropriate for use inpapermaking, as well as combinations of starch types, dextrin types, andcombinations of starches and dextrins. In certain embodiments, thebarrier substance 26 may include, but not is limited to additives suchas insolubilizers, lubricants, dispersants, defoamers, crosslinkers,binders, surfactants, leveling agents, wetting agents, surfaceadditives, rheology modifiers, non-stick agents, and other coatingadditives.

In certain embodiments, the hygroscopic substance 28 may comprise silica(e.g. silica nanoparticles). In other embodiments, the hygroscopicsubstance 28 may include, but is not limited to other hygroscopicreagents, activated charcoal, calcium sulfate, calcium chloride,molecular sieves, or other suitable water absorbing materials.

The weight ratio of the barrier substance 26 to the hygroscopicsubstance 28 may range from 99:1 to 1:99, and all ranges thereinbetween. In certain embodiments, weight ratio of the barrier substance26 to the hygroscopic substance 28 may further range from 25:75 to75:25. In yet other embodiments, the weight ratio of the barriersubstance 26 to the hygroscopic substance 28 may be approximately 50:50.

In certain embodiments, the particle size of the hygroscopic substance28 is determined in part by the amount of surface area needed to attractenough water to counteract the drop in release rate due to a reductionin the load level of the volatile composition 24. The hygroscopicsubstance 28 is also configured so that it will attract water vapor,rather than liquid water. As a result, the diameter of the particle sizeof the hygroscopic substance 28 may range from 0.001 μm-1 μm, and allranges therein between, and may further range from 1 nm-100 nm, whichwill attract the appropriate amount of water vapor molecules, as well asprovide a more even coating.

In certain embodiments, the hygroscopic substance 28 may have a surfacecharge range that ensures interaction with the barrier substances 26.For example, in the case of silica, the surface charge ranges from −10mV to −4000 mV, as measured by Zeta potential, which is a highly anionicpoint charge. When the silica is mixed with the maltodextrin beforecoating, the maltodextrin may group around the silica particles, whichmay further assist with the barrier formation within the modulatingcoating 14.

In certain embodiments, the modulating coating 14 may provide a moreconsistent release rate of the volatile compound 24. The consistency(variance) may be measured by the following formula.

Variance_((Weight-loss ratio))=First day weight-loss value/Last dayweight-loss value

A benefit of the modulating coating 14 is to reduce the variance withina ratio range of 1 to 20 over a life cycle of the article, which incertain embodiments may be 30 days, but could be longer or shorter asneeded or desired.

In certain embodiments, the modulating coating 14 may be used incombination with the porosity zones 1202 described above. For example,the modulating coating 14 may be applied to the external surfaces of thepulp base material 12 or may only be applied to the external surfaces ofthe low porosity zone 1208 to further enhance the regulating effect ofthe low porosity/high density design of that zone for top note volatilecomponents 24.

An additional benefit of the modulating coating 14 is the structuralreinforcement that the modulating coating 14 provides to the pulp basematerial 12, particularly for the high porosity zones 1206. In someembodiments, the modulating coating 14 may only be applied to theexternal surfaces of the high porosity zone 1206 to provide additionalstability to those high porosity zones 1206, even if the coating mayalso temper the release rate of base note volatile compositions 24 fromthe high porosity zones 1206.

D. Additional Treatment of the Base Material and/or Article

The base material 12 may be converted into the article 10, which mayoccur before or after the modulating coating 14 and/or the volatilecomposition 24 are applied.

In further embodiments, the article 10 may comprise a three-dimensionalstructure with varying shapes and sizes including but not limited to acylindrical disk, cylinder, tree, wreath, globe, orb, pine cone, star,bell, stocking, bag, gift box, snowman, penguin, reindeer, santa claus,heart, angel, basket, flower, butterfly, leaf, face, bird, fish, mammal,reptile, pyramid, cone, snowflake, other polygonal shape, fan blade or aportion thereof. The article 10 may have one or more flat surfaces,concave surfaces, convex surfaces, surfaces that are smooth, and/orsurfaces that contain complex geometry (e.g., peaks and valleys), or anyother suitable surface configuration.

In certain embodiments, the article 10 may comprise a spiral woundpaper. The spiral winding process allows for the paper to be the same ordifferent for each layer formed by winding the paper one completerevolution around the axis of the structural component. For example, thearticle 10 may comprise a rod shape, formed by winding the pulp basematerial 12 around a vertical axis, so that a rod having a length longerthan its diameter is formed. Each layer formed by the completerevolution of the paper matrix around the axis may be referred to as aply. For example, a 10 ply rod may have from one to ten differentcharacteristics for each ply of the rod. Characteristics may include butare not limited to absorbance, tensile strength density, pH, porosity,and polarity of the base material 12, and the type of paper or internalstructure 20.

The modulating coating 14 may be applied to the pulp base material 12before or after application of the volatile composition 24.

The modulating coating 14 may be applied to pulp base material 12 afterit has been removed from the mold 1204 and/or after it has been formedinto the article 10.

For example, the modulating coating 14 may be applied to the pulp basematerial 12 and/or the article 10 via a dip method where thethree-dimensional article 10 is placed within a volume of modulatingcoating 14 for a specified amount of time, then removed and allowed todry. The dip method may also be used with two-dimensional versions ofthe article 10. The add-on level may range from 0.1% to 10% by weight.

In other embodiments, the modulating coating 14 may be applied to thepulp base material 12 and/or the article 10 via an infusion method withthe add-on infusion ranging from 1% to 20% by weight, and, in certainembodiments, may further range from 10% to 20% by weight.

In yet other embodiments, the modulating coating 14 may be applied topulp base material 12 and/or the article 10 via spray treatment.

The volatile composition 24 may be applied to the base material 12before or after application of the modulating coating 14, as describedabove. For example, the volatile composition 24 may be applied byplacing the base material 12 and/or the article 10 in intimate contactwith the volatile composition 24 for a period of time. The volatilecomposition 24 may be in any physical state, such as liquid, solid, gel,or gas. For convenience, a liquid volatile composition 24 is described,but this is not intended to be limiting. The interaction time may dependon the concentration or type of volatile composition 24 being applied tothe base material 12 and/or the article 10, and/or how strong or intenseof a volatile composition 24 release is desired, and/or the type of basematerial 12. The saturation time (interaction time) may range from lessthan one minute to a several hours, to several days. The base material12 and/or the article 10 may be pre-treated prior to exposure to thevolatile composition 24. For example, the base material 12 and/or thearticle 10 may be placed in a drying oven to remove any residualmoisture. Further method steps comprise pressure treating and/or vacuumtreating the base material 12 and/or the article 10. After treatment,the base material 12 and/or the article 10 may be dried, for example byrubbing or patting dry, and/or by other methods known for drying asurface, and/or may be left to air dry. Drying steps may be used beforeor after other steps described herein.

In some embodiments, a method for applying the volatile composition 24to the base material 12 and/or to the article 10 comprises combining thevolatile composition 24 and the base material 12 and/or the article 10in a container and applying a pressure above atmospheric pressure on thevolatile composition 24 and base material 12 and/or the article 10.Pressure may be applied in a range from about 1 psi to about 40 psi,from about 5 psi to about 30 psi, or from about 10 psi to about 20 psi,at about 5 psi, at about 10 psi, at about 15 psi, at about 20 psi, atabout 25 psi, at about 30 psi, at about 35 psi, at about 40 psi, and/orat pressures therein between. The pressure may be applied for a periodof time from about 1 minute to about 10 hours, for about 30 minutes, forabout 1 hour, for about 2 hours, for about 3 hours, for about 4 hours,for about 5 hours for about 6 hours, for about 7 hours, for about 8hours, for about 9 hours, for about 10 hours, or longer if needed toapply sufficient amounts of the volatile composition 24 to the basematerial 12 and/or the article 10 to achieve a desired load of thevolatile composition 24 to the base material 12 and/or the article 10 orrelease of the volatile composition 24 from the base material 12 and/orthe article 10. Appropriate pressures and times for a particularembodiment can be determined by one skilled in the art based on theidentities and characteristics of the particular volatile composition 24and base material 12 and/or article 10.

In certain embodiments, a method for applying the volatile composition24 comprises combining the volatile composition 24 and base material 12and/or the article 10 in a container and applying a vacuum belowatmospheric pressure to the volatile composition 24 and the basematerial 12 and/or the article 10. Vacuum may be applied in a range from0.001 mm Hg to about 700 mm Hg, or from about 5 Kpa to about 35 kPa,from about 10 Kpa to about 25 kPa, from about 20 Kpa to about 30 kPa,from about 15 Kpa to about 25 kPa, from about 25 Kpa to about 30 kPa, atabout 5 kPa, at about 6 kPa, at about 7 kPa, at about 8 kPa, at about 9kPa, at about 10 kPa, at about 15 kPa, at about 16 kPa, at about 17 kPa,at about 18 kPa, at about 19 kPa, at about 20 kPa, at about 22 kPa, atabout 24 kPa, at about 26 kPa, at about 28 kPa, at about 30 kPa, andvacuums therein between. The vacuum may be applied for a period of timefrom about 1 minute to about 10 hours, for about 30 minutes, for about 1hour, for about 2 hours, for about 3 hours, for about 4 hours, for about5 hours for about 6 hours, for about 7 hours, for about 8 hours, forabout 9 hours, for about 10 hours, or longer if needed to applysufficient amounts of the volatile composition 24 to the base material12 and/or the article 10 to achieve a desired load of the volatilecomposition 24 to the base material 12 and/or the article 10 or releaseof the volatile composition 24 from the base material 12 and/or thearticle 10.

In yet other embodiments, the method may comprise pressure and vacuumsteps. The volatile composition 24 and the base material 12 and/or thearticle 10 may be combined and undergo vacuum treatment and pressuretreatment, in no particular order. For example, the volatile composition24 and the base material 12 and/or the article 10 may be combined in acontainer in an air-tight apparatus and a vacuum of 20 mm Hg to 80 mm Hgmay be applied for about 1 minute to 10 hours. Pressure treatment of 1psi to 40 psi may be applied for about 1 minute to about 10 hours andthe time and amount of vacuum or pressure treatment may vary and dependupon the amount of volatile composition 24 to be loaded in the basematerial 12 and/or the article 10, the type of base material 12 used,the intended use of the article 10, and other characteristics of thearticle 10.

In certain embodiments, the base material 12 and/or the article 10 maybe pre-treated with colorants, followed by treatment with the modulatingcoating 14. Colorants may include natural and synthetic dyes,water-resistant dyes, oil-resistant dyes, oil soluble dyes, andcombinations of water- and oil-resistant dyes. Colorants may be selectedbased on the composition of the base material 12, and is well within theskill of those in the art. Suitable water-resistant colorants includeoil soluble colorants and wax soluble colorants. Examples of oil solublecolorants include Pylakrome Dark Green and Pylakrome Red (Pylam ProductsCompany, Tempe Ariz.). Suitable oil-resistant colorants include watersoluble colorants. Examples of water soluble colorants include FD&C BlueNo. 1 and Carmine (Sensient, St. Louis, Mo.). A Lake type dye may alsobe used. Examples of Lake dyes are Cartasol Blue KRL-NA LIQ and CartasolYellow KGL LIQ (Clariant Corporation, Charlotte, N.C.). Pigments mayalso be used in coloring the base material 12 and may be added during orafter the manufacture of the base material 12. Such coloring or dyingmethods are known to those skilled in the art, and any suitable dyes,pigments, or colorants are contemplated by the present invention.Colorants may be used to affect the overall surface charge of the silicaor other hygroscopic substance 28 to enhance the interaction with thecoating.

In certain embodiments, ink or paint may be applied to the surface ofthe article 10 to provide complex designs, such as those shown in FIGS.21, 28, 30A-30B, 33A-33B, 37-39, 51-55. Such techniques are similar tothose used to apply ink or paint to ceramic materials. The ink or paintmay be applied in combination with dyes and/or in lieu of the dyeprocess.

E. Solvent-Free Fragrance Dispenser

According to certain embodiments, the article 10 is formed ofall-natural, biodegradable, recyclable, compostable and sustainablysourced materials, such as wood pulp. These materials are combined withall-natural biodegradable, recyclable, compostable performance boosters,such as silica, starch, and baking soda. The product is then treatedwith fragrance, such as 100% pure fragrance in the form of all-naturalessential oils and/or other responsibly selected and harvested fragrancematerials.

Specifically, the article 10 does not include a chemical solvent.Chemical solvents minimize the amount of fragrance that can be used (byas much as 85%) and compromise duration. Furthermore, chemical solventshave a chemical overtone that is difficult to entirely overcome withperfume. Use of chemical solvents means that it is impossible tocompletely eliminate carcinogens, respiratory sensitizers, asthmagens,phthalates and persistent bio-accumulative toxins, which lead to acompromised health and wellness profile.

Different arrangements of the components depicted in the drawings ordescribed above, as well as components and steps not shown or describedare possible. Similarly, some features and sub-combinations are usefuland may be employed without reference to other features andsub-combinations. Embodiments of the invention have been described forillustrative and not restrictive purposes, and alternative embodimentswill become apparent to readers of this patent. Accordingly, the presentinvention is not limited to the embodiments described above or depictedin the drawings, and various embodiments and modifications may be madewithout departing from the scope of the claims below.

1. An article comprising a pulp base material comprising fibers, whereinpores are formed between the fibers; and a volatile compositioncomprising at least one top note component and at least one base notecomponent; wherein the volatile composition at least partially fills thepores of the pulp base material; wherein a release rate of the at leastone top note component is modulated by the pulp base material; andwherein a release rate of the at least one base note component isenhanced by the pulp base material.
 2. The article of claim 1, whereinthe pulp base material comprises at least two zones with differentporosities including at least one low porosity zone and at least onehigh porosity zone.
 3. The article of claim 2, wherein the at least onetop note component is added to the at least one low porosity zone, andthe at least one base note component is added to the at least one highporosity zone.
 4. The article of claim 2, wherein the at least one lowporosity zone and the at least one high porosity zone are formed by useof a mold having different drainage surfaces.
 5. The article of claim 2,wherein the at least one low porosity zone and the at least one highporosity zone are formed by use of a divider within a mold.
 6. Thearticle of claim 2, wherein the at least one low porosity zone and theat least one high porosity zone are formed by application of differentpressures to portions of a mold.
 7. The article of claim 2, wherein theat least one low porosity zone and the at least one high porosity zoneare formed by application of different pulp concentrations to portionsof a mold.
 8. The article of claim 2, wherein the at least one lowporosity zone and the at least one high porosity zone are formed byapplication of different amounts of gas or gas-forming materials toportions of the pulp base material. 9-10. (canceled)
 11. The article ofclaim 1, wherein the pulp base material comprises at least one surfacehaving complex geometry, wherein the complex geometry comprises peaksand flatter regions.
 12. (canceled)
 13. The article of claim 11, whereinthe peaks enhance the release rate of the volatile composition.
 14. Thearticle of claim 11, wherein the peaks provide three-dimensionalemission of the volatile composition.
 15. The article of claim 1,wherein the article comprises an attachment element. 16-18. (canceled)19. The article of claim 1, further comprising a backing layer added tothe article, wherein the backing layer is formed of a conductivematerial.
 20. (canceled)
 21. The article of claim 1, further comprisingan opening through the article for placement of a light source.
 22. Thearticle of claim 1, wherein the pulp base material comprises a firstporosity and openings in which other materials having at least a secondporosity are added to the pulp base material.
 23. The article of claim2, wherein a modulating coating is applied to the pulp base material.24. The article of claim 23, wherein the modulating coating is onlyapplied to the at least one low porosity zone.
 25. The article of claim23, wherein the modulating coating is only applied to the at least onehigh porosity zone.
 26. The article of claim 1, wherein the article iscombined with at least one energy source, wherein the at least oneenergy source includes at least one from the group of a warmer bowl, aplate, and a fan. 27-32. (canceled)
 33. The article of claim 2, wherein:the volatile composition is mixed with a dye before at least partiallyfilling the pores of the pulp base material such that the at least twozones with different porosities each have a different visual appearance;and the at least one low porosity zone has a darker color based on acolor of the dye while the at least one high porosity zone has a colorsimilar to the pulp base material without the dye.
 34. (canceled)